No.104
Phosphorylation
| D2624 | Dibenzyl N,N-Diisopropylphosphoramidite (1) |
5g |

The present reagent 1 reacts rapidly with alcohols in the presence of 1H-tetrazole at room temperature to generate phosphorous triesters. Subsequent reaction with oxidizing agents such as m-chloroperoxybenzoic acid affords the corresponding phosphoric triesters 2. The triesters thus obtained can be deprotected by cleavage of the benzyl group by catalytic hydrogenolysis using Pd/C to yield the desired derivatives of phosphoric acids 31). The reagent 1 has high reactivity and its reactions to proceed under mild conditions. It has a wide scope of applications, including the synthesis of biomolecules such as oligonucleotides2).
References
1) Phosphorylation of cyclitols
K.-L. Yu, B. Fraser-Reid, Tetrahedron Lett., 29, 979 (1988).
2) The synthesis of oligonucleotides
S. L. Beaucage, R. P. Iyer, Tetrahedron, 48, 2223 (1992).
3) Other applications
a) Phosphorylation of amino acids
W. Bannwarth, A. Trzeciak, Helv. Chim. Acta, 70, 175 (1987).
b) Phosphorylation of peptides
J. W. Perich, R. B. Johns, Tetrahedron Lett., 29, 2369 (1988).
c) Phosphorylation of sugars
Y. Ichikawa, M. M. Sim, C.-H. Wong, J. Org. Chem., 57, 2943 (1992).
K.-L. Yu, B. Fraser-Reid, Tetrahedron Lett., 29, 979 (1988).
2) The synthesis of oligonucleotides
S. L. Beaucage, R. P. Iyer, Tetrahedron, 48, 2223 (1992).
3) Other applications
a) Phosphorylation of amino acids
W. Bannwarth, A. Trzeciak, Helv. Chim. Acta, 70, 175 (1987).
b) Phosphorylation of peptides
J. W. Perich, R. B. Johns, Tetrahedron Lett., 29, 2369 (1988).
c) Phosphorylation of sugars
Y. Ichikawa, M. M. Sim, C.-H. Wong, J. Org. Chem., 57, 2943 (1992).
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